1-amino-2-bromo-4-arylaminoanthraquinone compounds



, United States Patent l-AMINO-Z-BROMO-4-ARYLAMINOANTHRA- QUIN ONECOMPOUNDS James M. Straley and Ralph R. Giles, Kingsport, Tenu.,assignors to Eastman Kodak Company, Rochester, N.Y., a corporation ofNew Jersey No Drawing. Filed Aug. 28, 1958, Ser. No. 757,680

8 Claims. (Cl. 260-377) This invention relates to new anthraquinonecompounds and their application to the art of dyeing or coloring.

It is well known that polyacrylonitrile fibers are ditiicult to dye indeep, fast shades without the use of special dyeing techniques, such as,for example, the use of pressure, carriers or the so-called cuprous iontechnique involving the use of acid wool dyes. Each of these methodsinvolves one or more disadvantages. The use of pressure involves the useof pressure equipment which is more expensive than the equipment usedwhere no pressure is involved. The use of carriers involves the expenseof providing the carriers. Also, when carriers are employed operationsfor the recovery of the carrier for reuse are involved and theserecovery operations add to the expense of the dyeing operation.

While many variations in the cuprous ion technique have been proposedall sufi'er some disadvantage. One of the chief disadvantages of thismethod is the fact that it is almost impossible to restrict the amountof copper absorbed to such a low degree that serious browning of thedyed fabric upon exposure to light does not occur.

It is an object of our invention to provide dyes which can be readilyapplied to the polyacrylonitrile fibers, especially modifiedpolyacrylonitrile fibers, from ordinary dyebaths. That is, the dyes infinely divided condition are intimately dispersed in water and applieddirectly to the fiber. Another object of our invention is to providedyes which yield dyeings on polyacrylonitrile textile materials whichhave excellent fastness to light and washing. A further object of ourinvention is to provide dies which are capable of dyeingpolyacrylonitrile textile materials in deep shades.

The new anthraquinone compounds of our invention by means of which theobjects of our invention can be accomplished have the formula:

C\ Br 2 o ooiionnnn l e-@ Rx wherein R and R each represent an alkylgroup having 1 to 4 carbon atoms, a hydroxy alkyl group having 1 to 4carbon atoms, a l3-methoxyethyl group or a fi-ethoxyethyl group, nrepresents 2, 3 or 4 and wherein taken together also represent amorpholinyl group or a piperidyl group.

Ethylene, trimethylene, propylene, tetramethylene and Z-methyltrimethylene:

2,968,661 Patented Jan. 17, 1961 for example, are illustrative of thealkylene radicals rep resented by C H The new anthraquinone compounds ofour invention readily dye polyacrylonitrile textile materials and yieldblue dyeings thereon which have excellent fastness to light and washing.They are conveniently applied directly to the polyacrylonitrile textilematerial from an aqueous dispersion. Deep blue shades can be obtained onpolyacrylonitrile textile materials with the new anthraquinone compoundsof the invention. Verel and Orlon are illustrative of thepolyacrylonitrile materials that can be dyed.

While the anthraquinone compounds of our invention can be prepared bymore than one method We prefer to prepare them by condensing the acidchloride of the appropriate 1 amino 2bromo-4-carboxyanilinoanthraquinone with a primary amine having theformula:

R H:NCnH2nN i I wherein n, R, R and have the meaning previously assignedto them. The acid chloride of the1-amino-2-bromo-4-carboxyanilinoanthraquinone compound is prepared byknown methods.

The following examples illustrate the compounds of our invention andtheir manner of preparation.

Example 1 One gram of 1-amino-2-bromo-4-o-carboxyanilinoanthraquinonewas suspended in 20 cc. of dry chlorobenzene. Two cc. of thionylchloride were added and the reaction mixture obtained was heated on asteam bath, with stirring, until a clear solution was obtained and nofurther color change toward the red occurred. The solution thus obtainedwas cooled to C., diluted with an equal volume of n-hexane and cooled to20 C. The acid chloride thus prepared was recovered by filtration,washed with n-hexane and sucked dry. The acid chloride product thusobtained was added to 3.5 grams of 3- dimethylaminopropylamine and theresulting mixture was warmed on a steam bath to complete solution. Thereaction mixture was then poured into five times its volume of water andthe reaction product which precipitated was recovered by filtration anddried at 110 C. 0.95 gram of1-arnino-2-bromo-4-o-[N-(3-dimethy1aminopropyl)car- 'was obtained as ablue solid which dissolved readily warm dilute HCl. It dyespolyacrylonitrile fibers blue shades having excellent fastness to lightand wet processing. I

Example 2 Ten grams of 1-arnino-2-bromo-4-o-carboxyanilinoanthraquinonewere suspended in cc. of dry o -dichlorobenzene. 3.4 cc. .of'thionylchloride were added and the temperature, ofthe reaction mixture.was-gradually raised to 80 C. over a period of about 1.5 hours and heldat this temperature for one hour While stirring. Excess thionyl chloridewas :removed by passing a stream of dry air through the reaction mixtureat 65 70 C. After cooling the reaction mixture to room temperature 2.8grams of 3edimethylaminopropylarriine and 2.26 grams of anhydroussodiumacetate .were added and the reaction mixture was stirred at 70" C.'7S C.for one hour. The reaction mixture was cooled and the product whichprecipitated was recovered by filtration, washed with n-hexane and thenwith hot water and dried at 110 C. 11.3 grams of product identical withthat prepared in Example 1 were obtained.

Example 3 Example 1 was repeated using 4 grams of Z-dirnethyl-'aminoethylamine in place of 3-dimethylaminopropylamine. 'l-am'ino -'2bromo-- 4-o-[N-(2-dimethy'laminoethyl) carboxamido] anilinoanthraquinonewas obtained as a blue solid. It dyes polyacrylonitrile textilematerials blue shades which have excellent fastness to light and wetprocessing.

H l-amlno-Z-bromoA-p-(C ONCHqCHz CHiN Exam p [a 4 Example 1 was repeatedusing 1 gram of l-amino-Z- bromo-4-m-carboxyanilinoanthraquinone and 3.5grams of 3-dimethyl-aminopropylamine. l-amino-2-bromo-4- m [N (3dimethylaminopropyl)carboxamido]anilinoanthraquinone was obtained as ablue solid. It dyes polyacrylonitrile textile materials blue shadeswhich have excellent fastness to light and wet processing.

Example '5 Example 1 was .repeated using 1 gram of l-amino-2-bromo-4-p-carboxyanilinoanthraquinone and 3.5 grams of'3-dimethylaminopropy1amine. 1-amino-2-brorno-4-p-[N- (3dimethylaminoprqpyl) carboxamido] anilinoanthraquinone was obtainedas ablue solid. It dyes polyacrylonitrile textile materials blue shadeswhich have excellent fastness to .light and wet processing.

Example '6 Example 1 was repeated using 4.5 grams of3-diethylaminopropylamine in place of 3-dimethylaminopropylamine.l-amino-2-bromo-4-o-['N-(3-diethylaminopropyl) H l-amino-Z-bromo--o- CONCHQCHzCHIN carboxamido]anilinoanthraquinone was obtained as a bluesolid. It dyes polyacrylonitrile textile materials blue shades whichhave excellent "fastness to light and wet processing.

Example7 Example 1 was repeated using 1 gram of 1-amino-2-bromo-4sm-carboxyanilinoanthraquinone and 3 grams ofZ-diethylanfinoethylamine. l-amino-Z-bromol-m-[N-.(2-diethylaminoethyl)car.boxarnido] anilinoanthraquinone was obtained as ablue solid. .It dyes polyacrylonitrile textile materials blue shadeswhich have excellent fastness to light and wet processing.

Example 8 Example 1 was repeated using 1 gram of l-amino-Z-bromo-4-p-carboxyanilinoanthraquinone and 4 grams ofN-(Z-aminoethyllpiperidine. "l-amino-z-bromol-p-[N- (2-piperidylethyl)carboxamido] anilinoanthraquinone having'th'e formula:

(I? NH2 Example 1 was repeated using 1 gram of 1-amino-2-bromo-4-p-carboxyanilinoanthraquinone and 5 grams of3-(N-methyl-N-n-butyl)propylamine /CHa (HzNCHzCH2CH2N\ (34H!))anllinoanthraquinone 4 11 was obtained as a blue solid. It dyespolyacrylonitrile textile materials blue shades which have excellentfastness to light and wet processing.

Example 10 Example 1 was repeated using 6 grams of3-(di-fl-hydroxyethylamino)propylamine in place of3-dimethylaminopropylarnine.l-amino-2-bromo-4-o-[N-3-di-phhydroxyethylaminopropyl) carboxamido]anilinoanthraquinone was obtained as a blue solid. It dyespolyacrylonitrile textile materials blue shades which have excellentfastness to light and wet processing.

Example 11 Example 2 'was repeated using 3.3 grams of3-'('4-1norpholino) propylamine .H2 )H2 0-o in place of3-dimethylaminopropylamine.

"H2 H2 C-O O anilinoanthraquinone was obtained as a blue solid. It dyespolyacrylonitrile textile materials blue shades which have excellentfastness to light and wet processing.

Example 1 2 Example 4 was repeated using 4.1 grams of4-diethylamino-n-butylarrn'ne in place of S-dimethylaminopropylamine.1-amino-2-bromo-4-m-[N (4 diethylamino-nbutyl)carboxamido]anilino-anthraquinone was obtained as a blue solid. It dyespolyacrylonitrile textile materials blue shades which have excellentfastness to light and wet processing.

By the use of an equivalent amount of 4-dimethylamino-n-butylamine inplace of 4-diethylamino-n-butylamine, 1-amin0-2-bromo-4-m [N-.(-4-.'dimethylamino-nbutyl)carboxamidoLanilinoanthraquinone is obtainedas a blue solid. It dyes polyacrylonitrile textile materials blue shadeswhich have excellent fastness to light and wet processing.

Example 13 was obtained as a blue solid. It dyes polyacrylonitriletextile materials blue shades which have excellent fastness to light andwet processing.

Example 14 Example 2 was repeated using 3.4 grams of 3-(di- 8-methoxyethylamino)propylamine in place of 3-dimethy1- aminopropylamine.

CHzCHlOCHZ H l-amino-2-bromo4-o- O ONCHnCHgCHzN C H: Hz 0 G H;

was obtained as a blue solid. It dyes polyacrylonitrile textilematerials blue shades which have excellent fastness 30 to light and wetprocessing.

Example Example 2 was repeated using 4.6 grams of 3-(di-18- Example 1616.7 milligrams of the dye compound prepared in Example 1 was dissolvedby warming in 5 cos. of ethylene glycol monomethyl ether. 20 ccs. of a1% aqueous solution of Igepon T (3113 (Or- H 0 ONCH CHzSOaNa) were addedand the volume brought to 200 ccs. by the addition of water at 50 C.Five cos. of a aqueous solution of formic acid were added, followed by 5grams of Verel fabric. The temperature was brought to the boil and heldthere for 1 hour. The cloth was then rinsed in hot water and allowed todry. It was dyed an attractive blue shade having excellent wash andlight fastness. Similar results are obtained when Orlon 42 fabric isused instead of Verel fabric.

The primary amine compounds having the Formula I used in preparing thenew anthraquinone compounds of the invention appear to include new aswell as old comjlanilinoanthraquinone pounds. Many of these amines arespecifically disclosed in the prior art. Those not specificallydisclosed can be prepared by the methods used to prepare the knowncompounds. The preferred amine 3-dimethylaminopropylamine is an articleof commerce.

Three general processes by which primary amineshavethoxyethylamino)propylamine in place of S-dimethyling the formula Ican be prepared are set forth hereinornomo cm,

was obtained as a blue solid. It dyes polyacrylonitrile textilematerials blue shades which have excellent fastmess to light and wetprocessing.

Other primary amines that can be used to prepare compounds of ourinvention include, for example Z-di-n-propylaminoethylamine,Z-diisopropylaminoethylaming 2-di-n butylaminoethylamine,

2-( di-fl-hydroxyethylamino) ethylamine, Z-(di-fi-ethoxyethylaminoetllylamine,

3-( di-fl-hydroxypropylamino propylamine, 3-(di-fi-hydroxybutylamino)propylamine, 4-(di-5-hydroxyethylamino) butylamine and 4-(4'-morpholino)propylamine. i

The new anthraquinone compounds of our invention can be applied topolyacrylonitrile textile materials from an aqueous dyebath in the samemanner that water-insoluble cellulose acetate dyestulfs are commonlyapplied to cellulose acetate textile materials. Thus they may bedirectly applied to the polyacrylonitrile textile material undergoingcoloration in the form of an aqueous suspension which can be prepared bygrinding them to a paste in the presence of a sulfonated oil, soap,sodium lignin sulfonate, or other suitable dispersing agent anddispersing the resulting paste in water. As previously indicated thedyes should be in finely divided condition.

The following example illustrates how the anthraquinone compounds of ourinvention can be applied to polyacrylonitrile textile materials. Asnoted hereinbefore the anthraquinone compounds are particularly usefulin connection with the dyeing of modified polyacrylonitrile textilematerials, such as Verel.

after:

:lanilinoantlnaquinone (1) an amine having the formula:

R1 II is condensed with a chloroalkylnitrile having the formula: Cl(CHCN, and the product obtained is reduced by sodium-alcohol or withhydrogen over Raney nickel to give the desired product:

(2) Potassium phthalimide is condensed with a dibromoalkyl compoundhaving the formula: Br(CH Br to obtain C H (CO) N(CH Br which is treatedwith II to give which is hydrolyzed with dilute mineral acid to giveHzN(CH2) IN the desired product. Method 2 is the well-known Gabrielsynthesis.

(3) A secondary amine is added to an unsaturated nitrile, e.g.methacrylonitrile, and the product hydrogenated to the primary amine:NH,

II I R R\ Br NOHzCHCN--- NCHzOHOH NHg 6 R1 CH3 R1 CH3 0113 on; N I HHgNCHgCHCHzN CH3 L H CH3 ONOHzCHaCHzN and CH3 OH; 02115 5. Theanthraquinone compound having the formula:

I HzNCHzOHOHgN NH;

for example, can be readily prepared by method 3 by reactingdimethylamine and diethylamine, respectively,

with methacrylonitrile and then hydrogenating the products obtained totheir primary amine form. 0

0Hv R J7 H t ONCHZGHZN R, R1 and N \R CH3 i 6. The anthraquinonecompound having the formula:

as used herein have the meaning previously assigned to 0 NH:

CHa H ?ONCH2CH2CHEN\ O N H 7. The anthraquinone compound having theformula:

R1 CH: 8. The anthraquinone compound having the formula:

wherein R and R each represents a member selected from the groupconsisting of an alkyl group having 1 to 4 carbon atoms, a hydroxyalkylgroup having 1 to 4 carbon atoms, a fi-methoxyethyl group and afl-ethoxyethyl group, n represents a whole number selected from 2, 3 and4 and wherein taken together also represent a member selected from thegroup conslstmg of a morpholinyl group and a References Cited in thefile of this patent peridyl group.

2. The anthraquinone compounds of claim 1 wherein R UNITED ATES PATENTSand R each represents an alkyl group having 1 to 4 car- 7 5 5 Boyd Aug30, 1955 bon atoms.

3. The anthraquinone compounds of claim 2 wherein FOREIGN PATENTS C H is-CH CH CH 855,541 Germany Nov. 13, 1952 4. The anthraquinone compoundhaving the formula:

1. THE ANTHRAQUINONE COMPOUNDS HAVING THE FORMULA: